Hair spray containing esters of maleic anhydride interpolymers

ABSTRACT

Water-insoluble alkyl half ester interpolymers and waterinsoluble ammonium and amine salts thereof, and hair spray compositions made therefrom; said interpolymers consisting essentially of the structural units:   OBTAINED BY INTERPOLYMERIZING MALEIC ANHYDRIDE WITH TWO DIFFERENT ALKYL VINYL ETHERS, R1-O-CH Ch2 and R2-O-CH CH2, followed by partial esterification with an alkanol having 1 to 8 carbon atoms. The esterification can be followed by neutralization of free carboxyl groups with ammonia, a primary, secondary, or tertiary alkylamine, alkanolamine, or alkylalkanolamine of the formula   WHERE Z1, Z2, and Z3 are all hydrogen to make up ammonia, where Z1, Z2, and Z3 are individually selected from the group consisting of hydrogen and of alkyl radicals, having 1 to 18 carbon atoms to make up the alkylamine, where Z1, Z2, and Z3 are individually selected from the group consisting of hydrogen and of hydroxyethyl and hydroxypropyl radicals to make up the alkanolamine, or where Z1, Z2, and Z3 are mixtures of alkyl and hydroxyalkyl groups as described to make up the alkylalkanolamine, to give the ammonium or amine salts of the interpolymers. R1 Alkyl radical, 8 to 18 carbon atoms; R2 Alkyl radical, 1 to 3 carbon atoms; X and Y are individually selected from the group consisting of (1) alkoxy, 1 to 8 carbons atoms, and (2) hydroxy. The ammonium or amine salts of the foregoing compounds (when X or Y represents a hydroxy radical) are salts of ammonia or of those amines described above.

United States Patent 1191 Block et al.

[ HAIR SPRAY CONTAINING ESTERS OF MALEIC ANIIYDRIDE INTERPOLYMERSInventors: Ira Jordan Block; Phillip Edward Sokol, both of Chicago, Ill.

The Gillette Company, Boston,

Mass.

Filed: May'8, 1972.

Appl. No.: 251,362

[73] Assignee:

US. Cl. .1 424/47, 260/785 T, 424/7 Int. Cl A6lk 7/10 Field of Search424/47; 260/785 T, 71

[56] References Cited UNITED STATES PATENTS 4/1965 Zoebelein, 424/477/1968 Hsiung 424/47 4/1969 Azorlosa et al. 260/785 T 8/1972 Field etal. 260/785 T 8/1972 Field et al. 260/785 T Primary Examiner-Albert T.Meyers Assistant Examiner-Norman A. Drezin [571 ABSTRACT Water-insolublealltyl half ester interpolymers and water-insoluble ammonium and aminesalts thereof, and hair spray compositions made therefrom; saidinterpolymers consisting essentially of the structural units:

Unit I obtained by interpolymerizing maleic anhydride with two differentalkyl vinyl ethers, R,OCH=Ch and R OCH=CH followed by partial,esterification with an alkanol having 1 to 8 carbon atoms.

1451 Jan. 21, 1975 The esterification can be followed by neutralizationof free carboxyl groups with ammonia, a primary, secondary, or tertiaryalkylamine, alkanolamine, or alkylalkanolamine of the formula where Z Zand Z are allhydrogen to make up ammonia, where 2,, Z and Z areindividually selected from the group consisting of hydrogen and of alkylR,=Alkyl radical, 8 to 18 carbon atoms; R .=Alkyl radical, l to 3 carbonatoms; X and Y are individually selected from the group consisting of 1)alkoxy, l to 8 carbons atoms, and (2) hydroxy. The ammonium or aminesalts of the foregoing compounds (when X or Y Unit i1 represents ahydroxy radical) are salts of ammonia or of those amines describedabove.

16 Claims, No Drawings HAIR SPRAY CONTAINING ESTERS OF MALEIC ANHYDRIDEINTERPOLYMERS This invention relates to novel water-insolublefilmforming derivatives of maleic anhydride interpolymers and to novelhair-setting compositions incorporating these derivativesof'interpolymers.

in the art of imparting a temporary set to a configuration of the hairto obtain a particular hair style by means of hair-setting compositionsor hair sprays, the desired effect is to have sufficient set-holding ofthe hair to withstand even adverse weather conditions such as brisk windor high humidity without making the hair excessively stiff, tacky, ordifficult to comb or without leaving flakes in the hair. Present hairsprays afford some set holding properties without accentuating theseundesired characteristics, but they do not approach effectiveset-holding under adverse weather conditions without imparting eitherexcessive stiffness, tack, or otherwise aggravating the aforementioned.unwanted properties.

One object of the present invention is to provide new compositions ofmatter.

A further object is to provide a hair-setting composition which displaysremarkably improved set-holding characteristics and which maintains thecoiffure in the desired configuration even under adverse conditions suchas high temperature and high humidity.

A further object is to provide a hair-setting composition whichmaintains the coiffure in the desired configuration without leaving thehair excessively stiff and inflexible.

Another object is to provide a hair-setting composition which retains adry non-tacky surface even when exposed to conditions of high humidity.

Still another object is to provide a hair-setting composition whichmakes it possible to comb the hair without difficulty.

A further object is to provide a hair-setting composition which iscapable of being homogeneously blended with gaseous or liquefied gaspressure propellants, particularly halogenated hydrocarbon propellants,in order to be dispensed from a pressure container in the form of anaerosol.

Other and further objects will be apparent from the description whichfollows.

The resins of this invention are certain waterinsoluble film-formingmodified interpolymers of maleic anhydride and two different alkyl vinylethers. More specifically, they are water-insoluble lower alkyl halfesters of maleic anhydride interpolymer compounds and water-insolubleammonium and amine salts thereof which are comprised of repeating groupsof the formula radical containing 1 to 8 carbon atoms and of (2) thehydroxy radical. The ammonium and amine salts of the foregoing compounds(when X or Y represents a hydroxy radical) are salts of ammonia, aprimary, secondary or tertiary alkylamine, alkanolamine, oralkylalkanolamine of the formula nolamine, or where Z Z and Z aremixtures of alkyl and hydroxyalkyl groups as described to make up thealkylalkanolamine. The proportion of alkoxy groups in the total numberof groups X and Y is from about 40 percent to about percent; there beingfrom about 0.01 to about 43 mole percent of Unit I andfrom'about 57 toabout 99.99 mole percent of Unit II'in the interpolymer.

Examples of the alkyl radical R are n-octyl, dodecyl,

hendecyl, tridecyl, tetradecyl, hexadecyl, and stearyl.

The members of the alkyl radical R group are methyl, ethyl, n-propyl,and isopropyl. Examples of the alkoxy radicals comprising one of thegroups from which X or Y is selected are methoxy, ethoxy, isopropoxy, n-

- pentoxy, hexoxy, and heptoxy.

The molecular weight of the instant anhydride interpolymers of thisinvention may be conveniently defined by their viscosity as an alcoholsolution of the alkyl half ester which can be measured using theBrookfieldViscometer. The interpolymers of this invention exhibit aBrookfield viscosity from about cps. to about 4,000 cps. at 25C and at30 percent concentration in ethanol using a No. 2 spindle with a 250 cc.breaker, the percentage being based on the weight of the total solution;those polymers giving a Brookfield viscosity from about 200 cps. toabout 3,000 cps. under the same conditions are preferred.

These novel water-insoluble derivatives of interpolymers can be preparedby conventional known methods by interpolymerizing maleic anhydride anda mixture of alkyl vinyl ethers using approximately one mole of maleicanhydride per mole of alkyl vinyl ether mixture.

H Cl-l "'CH iIH and HCH -'-CH'CH i O: (|)=O (L O=(L %=0 1 Y i, l Y

Unit I Unit I I wherein R, represents an alkyl radical containing 8 to18 carbon atoms, R is an alkyl radical having from one to three carbonatoms, and X and Y are each individually selected from the groupconsisting of l an alkoxy One class of alkyl vinyl ether may berepresented by the structural formula wherein R represents an alkylradical containing 8 to 18 carbon atoms, preferably a substantiallylinear (long chain) moiety. The other class of alkyl vinyl ether may berepresented by the structural formula wherein R represents an alkylradical containing 1 to 3 carbon atoms. The ratio of the R,OCH=CH alkylvinyl ether to the R O--CH=CH alkyl vinyl ether comprising the totalamount of such vinyl ether mixtures should be within the rangesmentioned above, i.e., from about 0.01 to about 43 mole percent of the ROCH=CH alkyl vinyl ether and from about 57 to about 99.99 mole percentof the R -OCH=CH alkyl vinyl ether. This ratio can also be defined interms of the relative weights of the two ethers in which case the rangeswould be from about 2 to about 75 weight percent of the R OCH=Cl-l etherand from about 25 to about 98 weight percent of the R- ,-OCH=CH ether,based on the total weight of the vinyl ether mixture.

The polymerization is carried out by adding a catalytic amount of anorganic free-radical-generating initiator to a mixture of the threemonomers in a diluent. The mixture is heated thoroughly so that thepolymerization reaction takes place to produce the anhydrideinterpolymer containing repeating units of the formula and wherein R andR are as above defined. When gas chromatographic analysis indicates nodetectable residual monomer, the polymer is postcooked and isolated fromthe diluent by any suitable means such as distillation.

The diluent selected can include benzene, xylene, toluene, acetone,methyl ethyl ketone, and the like. If desired, the reaction can also beconducted in an inert atmosphere such as nitrogen, argon and the like.

Suitable organic initiators include, for example, benzoyl peroxide,lauroyl peroxide, caprylyl peroxide, acetyl peroxide, acetyl benzoylperoxide, di-tert-butyl peroxide, dimethyl azobisisobutyrate,azobisisobutyronitrile, and the like. Radiation polymerization is alsosuitably conducted using initiators such as high energy radiationsources, for example, X-rays, gamma rays, ultraviolet light, neutrons,and the like.

The polymerization can be performed at a temperature within the range ofabout 0 to about 150C, preferably in the range from about 45 to about100C, particularly about 80C.

Conversion of this anhydride interpolymer contain ing repeating units ofthe formula of Units la and [la to the water-insoluble film-forming halfesters of this invention, Units I and II, is accomplished by reactingthe interpolymers with an alkanol containing from 1 to 8 carbon atomssuch as ethanol, isopropanol, n-butanol, pentanol, hexanol, or heptanol.Each anhydride group, upon reacting, forms (I) a carboxylic ester groupand, simultaneously, (2) a carboxylic acid group. The carboxylic acidgroups so formed can themselves be reacted to form additional estergroups. Consequently,

the modified interpolymer can be defined as one in which from 40 to 60percent, preferably about 50 percent, of the total carboxyl groups (thetotal which could be formed by hydrolysis of all the anhydride groups)present in the interpolymer are reacted to form esters, the remainingcarboxyl groups existing as free carboxyl groups.

The esterification of the interpolymers is a substantially spontaneousreaction where the half ester is desired. The reaction with the alkanolis best carried out by heating the mixture at reflux temperature. To beceratin that 50 percent of the total carboxyl groups (the total whichcould be formed by hydrolysis of all the anhydride groups) areesterified, the mixture may be heated up to 25 to 50 hours at refluxtemperature. Alternatively, infrared spectroscopy can be used todetermine the absence of anhydride units indicating total conversion tocarboxyl and carboxylic ester groups,

The esterification process can be started simultaneously with theremoval of the diluent as for example by azeotropic distillation of thebenzene diluent with ethanol. Continued refluxing in ethanol under theaforesaid conditions will give complete half ethyl ester formation. Thehalf ester is soluble in the alkanol used in the esterification. Thealkanol solution is then concentrated to a convenient form, about 30 to45 weight percent solids based on the total weight of the solution.

Additionally the free carboxyl groups can undergo neutralization inorder to produce the water-insoluble ammonium or amine salts of thisinvention. This neutralization can be carried out at room temperature byadding to the partial alkyl esters ammonia, a primary, secondary, ortertiary alkylamine, alkanolamine, or alkylalkanolamine of the formulawhere Z Z and Z are all hydrogen to make up ammonia, where 2,, Z and Zare individually selected from the group consisting of hydrogen and ofalkyl radicals, having 1 to 18 carbon atoms to make up the alkylamine,where Z Z and Z are individually selected from the group consisting ofhydrogen and of hydroxyethyl and hydroxypropyl radicals to make up thealkanolamine, or where Z Z and Z are mixtures of alkyl and hydroxylalkylgroups as described to make up the alkylalkanolamine, to give theammonium or amine salts of the interpolymers.

Where an alkylamine is utilized, suitable amines include primaryalkylamines having 1 to 18 carbon atoms such as ethylamine,n-propylamine, n-butylamine, nheptylamine, n-decylamine, laurylamine, orstearylamine; secondary alkylamines consisting of alkyl branches havingfrom 1 to 18 carbon atoms each such as dimethylamine, diisopropylamine,ethylisopropylamine, methyl-n-hexylamine, laurylmethylamine, ordioctylamine; and tertiary alkylamines consisting of alkyl brancheshaving from 1 to 18 carbon atoms each such as triethylamine,triisopropylamine, tri-n-butylamine, lauryldimethylamine,stearyldimethylamine, or trioctylamine. Stearyldimethylamine ispreferred.

Where an alkanolamine is utilized, suitable alkanolamines include mono-,di-, and tri-ethanolamine and isopropanolamine. Triethanolamine is thepreferred reagent.

Where an alkylalkanolamine is utilized, suitable alkylalkanolaminesinclude bis-hydroxyethylstearylamine, bis-hydroxypropyllaurylamine,hydro'xyethyldibutylamine, or hydroxypropyldioctylamine.

Of the remaining carboxyl groups which exist as free carboxyl groups,from about 5 to 50 percent can be neutralized to form the ammonium,alkylamine, alkanolamine, or alkylalkanolamine salts. Preferably fromabout to 20 percent can be neutralized.

The hair-setting compositions of this invention comprise the half esterinterpolymers and the ammonium and amine salts thereof described abovedissolved in an anhydrous alkanol containing from 1 to 8 carbon atomssuch as ethanol, n-propanol, isopropanol, the butanols, pentanol, andhexanol. The solution should contain from about 0.05 to 20 percent,preferably from 0.5 to 10 percent, by weight of the total solution, ofthe interpolymer.

While this solution of the film-forming material in the alkanol may beapplied to the hair by an atomizer or in any other suitable fashion, ithas been found most convenient to employ a gaseous or volatileliquid-propellant and to package the mixture of propellant with thealcoholic solution in a pressure package having a valvecontrolledoutlet. Any of the' usual propellants may be employed, such as propane,isobutane, or, preferably, the saturated halogenated aliphatichydrocarbons known by the trade name Freon and which include, forexample, l,l-difluoroethane; l,2-dichloro-l,l,2,2- tetrafluoroethane;trichlorotrifluoroethane; dichlorodifluoromethane;monochlorodifluoromethane; monofluorotrichloromethane; l-monochloro-l ldifluoroethane; or mixtures thereof. With the propellant included, thehalf ester and ammonium and amine salt interpolymers constitute fromabout 0.5 to about 10 percent by weight of the total composition;preferably from about 0.5 to about 4 percent. Similarly, the alkanolsolvent constitutes from about 35 to about 64.5 percent by weight of thetotal composition; preferably from about 45 to 54.5 percent. Theliquefied gas propellant constitutes from about 35 to 64.5 percent byweight of the total composition; preferably from about 45 to about 54.5percent.

Optionally, the composition can include conventional additives known inthe hair spray art such as a plasticizer, perfume, and a conditioningagent. Optional plasticizers may include such compounds as isostearylalcohol, diisopropyl adipate, dibutyl phthalate, and isopropyl stearate.The amount of plasticizer can vary from about 0.05 to about 20 percentby weight of the interpolymer; preferably about l to 20 percent.Preferably, based on the weight of the total composition, theplasticizer should range from about 0.05 to about 3 percent.

Minor amounts of other conventional additives such as lanolin to restorethe natural condition of the hair, liquid dimethyl polysiloxane for easein combing (from 1 to 20 percent by weight of the polymer), and analcohol soluble perfume for aesthetic appeal (from 0.1 to

about 1 percent by weight of the total composition) may also beincluded.

The following specific examples are intended to illustrate more clearlythe nature of the present invention without acting as a limitation uponits scope.

EXAMPLE 1 An interpolymer containing equimolar amounts of maleicanhydride and of a mixture of stearyl vinyl ether and ethyl vinyl etherin which 5 percent by weight of the ether mixture was stearyl vinylether and percent was ethyl vinyl ether was prepared as follows: Amixture of 262 parts by weight of maleic anhydride, 10 parts by weightof stearyl vinyl ether, and parts by weight of ethyl vinyl ether wasprepared to which was added lauroyl peroxide in an amount totaling 0.5percent by weight of the mixture. The monomer mixture containing theinitiator was added to 2,300 parts of refluxing benzene over a /2 hourperiod. Refluxing was continued an additional 1-2 hours. The'benzene wasthen removed, first by distillation and then finally by azeotroping itwith ethanol during which a portion of the interpolymer (in anhydrideform) was converted to the half ethyl ester. Continued refluxing inethanol resulted in complete half ester formation. Finally, the ethanolsolution was concentrated to about 30 to 40 percent polymer solids byweight of total solution.

The solution was then dilutedwith additional ethanol to form a mixtureof about 2 parts by weight of the interpolymer to 47.3 parts by weightof ethanol. To this mixture there was added 0.3 parts by weight ofisopropyl stearate, 0.3 parts by weight of stearyldimethylamine, and 0.1parts by weight of perfume. This solution was then charged into apressure container along with 32 parts by weight of Freon l l and 18parts by weight of Freon 12, the Freon propellants being maintained inliquefied form within the pressure container (pressure about 3640p.s.i.g.).

When sprayed on a hair tress held in a desired configuration and allowedto dry, the composition was found to provide good set-holdingcharacteristics even under conditions of high humidity while at the sametime leaving the hair neither excessively stiff, tacky, nor powdery.

EXAMPLE 2 A half ethyl ester interpolymer containing equimolar amountsof maleic anhydride and a vinyl ether mixture of 25 percent by weight ofstearyl vinyl ether and 75 percent by weight of ethyl vinyl ether wasprepared according to the procedures described in Example 1.

The interpolymer was then dissolvedin ethanol to the same concentrationas in Example 1, and the same additives in the same weight proportionswere added as in EXAMPLE 3 A half ethyl ester interpolymer containingequimolar amounts of maleic anhydride and a vinyl ether mixture of 75percent by weight of stearyl vinyl ether and 25 percent by weight ofethyl vinyl ether was prepared according to the procedures described inExample 1.

The interpolymer was then further diluted in ethanol, and a hair spraycomposition was prepared using the same weight proportions of polymer,ethanol, and the same conventional additives as in Example 1 with theexception that 0.45 parts by weight of diisopropyl adipate were usedinstead of the isopropyl stearate. The solution was charged into apressure container along with volatile propellants as described inExample 1 above. When sprayed on a hair tress, it was found to havesubstantially the same set-holding characteristics and otheraforementioned desirable characteristics as the composition of Example1.

EXAMPLE 4 In the same manner as outlined in Example 1, an ethyl halfester interpolymer was prepared containing equimolar amounts of maleicanhydride and a vinyl ether mixture of 25 percent by weight of cetylvinyl ether and 75 percent by weight of ethyl vinyl ether. The reactionsolution was then formulated into a hair spray in the same manner as inExample 1. Similar desirable set-holding characteristics were found uponuse.

EXAMPLE 5 In the same manner. as outlined in Example 1, an ethyl halfester interpolymer was prepared containing equimolar amounts of maleicanhydride and a vinyl ether mixture of 25 percent by weight of decylvinyl ether and 75 percent by weight of ethyl vinyl ether. The reactionsolution was then formulated into a hair spray perature or in a C ovenif speed is desired. The hair fibers are secured with a small bobbi pinat the backside of the curl, while the original large bobbi pin isremoved and the curler is carefully slid out of the curl. Each tress issprayed two seconds from approximately 8 inches with the particularhair-set composition to be tested. Usually samples are done in duplicateor triplicate. After the samples have air dried for 96 hour, the bobbipin is carefully removed and the samples are placed on a suspension rod.The initial curl fall is recorded in centimeters measuring from thebottom edge of the tress card to the bottom edge of the curl. Then thesamples are placed in an 85 percent relative humidity chamber or ifdesired in the percent relative humidity room. The samples are removedfor recording data after 2 hours, 4 hours, and overnight exposure. Therelative curl fall may be easily calculated if the control spray isgiven a value of 1.0.

Upon testing as described above all of the compositions of the presentinvention exhibited substantially the same set-holding capabilitytogether with desirable softness of the treated hair. There was noevidence of flaking or powdering in the case of the compositions of thepresent invention and little or no tendency to exhibit any tackinessupon exposure to conditions of high relative humidity.

What is claimed is:

l. A hair spray composition comprising a solution in an alkanol having 1to 8 carbon atoms, said solution containing from 0.05 to 20 percent byweight based on the weight of the total solution of a water-insolubleinterpolymer consisting essentially of the structural units:

CH Cl-l CH- (IIH ----and Cl-l- CH C|IH (|IH'-- O O= C C=O O O=C C=O l ll l I I R X Y R X Y Unit 1 Unit I I in the same manner as in Example 1.Similar desirable 45 wherein R represents an alkyl radical having from 8to set-holding characteristics were found upon use.

Similar results as regards set-holding were obtained using solutionsprepared as described above, containing the waterinsoluble ethyl halfesters of interpolymers composed of equimolar amounts of maleicanhydride and the following vinyl ether mixtures:

l. 25 percent by weight of isooctyl vinyl ether and percent by weight ofethyl vinyl ether.

2. 25 percent by weight of stearyl vinyl ether and 75 percent by weightof methyl vinyl ether.

3. 25 percent by weight of lauryl vinyl ether and 75 percent by weightof ethyl vinyl ether.

4. 25 percent by weight of stearyl vinyl ether and 75 percent by weightof n-propyl vinyl ether. The percentage of each ether is based on thetotal weight of the mixture of the two alkyl vinyl ethers used in eachcase.

The set-holding properties of the hair-setting compositions of thepresent invention were tested by the following procedure:

Moderately wet 5 inch tresses of straight hair are wrapped around a inchdiameter curler and secured with a large bobbi pin. Tresses are dried atroom tem- 18 atoms; wherein R represents an alkyl radical having from 1to 3 carbon atoms; and wherein X and Y each independently represent aradical'selected from the group consisting of (1) an alkoxy radicalhaving from 1 to 8 carbon atoms and (2) the hydroxy radical; theproportion of alkoxy radicals in the total number of X and Y radicalsbeing from about 40 to about 60 percent; there being from about 0.01 toabout 43 mole percent of Unit I and from about 57 to about 99.99 molepercent of Unit [I in the interpolymer, based on the total number ofmoles of structural Units I and II in the interpolymer; and wherein saidinterpolymer, in the form of a 30 percent by weight solution in ethanolat 25C. exhibits a Brookfield viscosity from about cps. to about 4,000cps. using a No. 2 spindle with a 250 cc. beaker.

2. A hair spray composition as claimed in claim 1 in which from about 5to 50 percent of the free carboxyl groups of said interpolymer have beenneutralized by a member of the group consisting of ammonia, primary,secondary, and tertiary alkylamines, alkanolamines andalkylalkanolamines of the formula where Z Z and Z, are all hydrogen tomake up ammonia, where Z,, Z and Z are individually selected from thegroup consisting of hydrogen and of alkyl radicals having 1 to 18 carbonatoms to make up the alkylamines, where Z,, Z and Z, are individuallyselected from the group consisting of hydrogen and of hydroxyethyl andhydroxypropyl radicals to make up the alkanolamines, and where Z Z andZ, are mixtures of said alkyl and hydroxyalkyl groups to make up saidalkylalkanolamines, to give the ammonium, alkylamine, alkanolamine oralkylalkanolamine salts of said interpolymer.

3. A hair spray composition as claimed in claim 1 in which said alkanolis ethyl alcohol, wherein R is stearyl, R is ethyl and said alkoxyradical is ethoxy.

4. A hair spray composition as claimed in claim 3 wherein from about topercent of the free carboxyl groups of said interpolymer have beenneutralized by a member of the group consisting of ammonia, primary,secondary, and tertiary alkylamines, alkanolamines andalkylalkanolamines of the formula where 2,, Z and Z are all hydrogen tomake up ammonia, where Z Z and Z, are individually selected from thegroup consisting of hydrogen and of alkyl radicals having 1 to 18 carbonatoms to make up the alkylamines, where Z Z and Z are individuallyselected from the group consisting of hydrogen and of hydroxyethyl andhydroxypropyl radicals to make up the alkanolamines, and where Z Z andZ, are mixtures of said alkyl and hydroxyalkyl groups to make up saidalkylalkanolamines, to give the ammonium, alkylamine, alkanolamine oralkylalkanolamine salts of said interpolymer.

5. A package comprising a closed container valve-controlled outletholding a composition fined in claim 1 together with a propellant.

6. A package comprising a closed container valve-controlled outletholding a composition fined in claim 2 together with a propellant.

7. A package comprising a closed container valve-controlled outletholding a composition fined in claim 3 together with a propellant.

8. A package comprising a closed container valve-controlled outletholding a composition fined in claim 4 together with a propellant.

9. A package as defined in claim 7 in which said composition includesisopropyl stearate in an amount from about 0.05 to about 20 percent ofthe weight of the interpolymer used in said package.

10. A package as defined in claim 8 in which said with a as dewith a asdewith a as dewith a as decomposition includes isopropyl stearate in anamount from about 0.05 to about 20 percent of the weight of theinterpolymer used in said package.

11. A hair spray composition comprising an ethyl alcohol solutioncontaining from about-0.05 to about 20 percent by weight of awater-insoluble partial ester of an interpolymer of equimolar amounts ofmaleic anhydride and a mixture of from 2 to 75 percent by weight ofstearyl vinyl ether and from 25 to 98 percent by weight of ethyl vinylether based on the total weight of the ether mixture, in whichinterpolymer from 40 to percent of the total carboxyl groups present insaid modified interpolymer are reacted with ethyl alcohol to form saidester; said interpolymer having a Brookfield viscosity from about 200cps. to 3,000 cps. using a No. 2 spindle at 25C. and at 30 percentconcentration in ethanol with a 250 cc. beaker, the percentage beingbased on the weight of the total solution.

12. A hair spray composition as defined in claim 11 wherein from about10 to 20 percent of the free carboxyl groups have further been reactedwith a member of the group consisting of ammonia, primary, secondary,and tertiary alkylamines, alkanolamines and alkylalkanolamines of theformula where Z Z and Z are all hydrogen to make up ammonia, where Z Zand Z are individually selected from the group consisting of hydrogenand of alkyl radicals having 1 to 18 carbon atoms to make up thealkylamines, where Z,, Z and Z are individually selected from the groupconsisting of hydrogen and of hydroxyethyl and hydroxypropyl radicals tomake up the alkanolamines, and where Z Z and Z, are mixtures of saidalkyl and hydroxyalkyl groups to make up the alkylalkanolamine.

13. A package comprising a pressure-tight container having avalve-controlled outlet and containing a hairsetting compositioncomprising:

a. about 35.5 to about weight percent, based on the total weight of thecomposition, of the solution defined in claim 11, and

b. about 35 to about 64.5 weight percent, based on the total weight ofthe composition, of a propellant.

14. A package as defined in claim 13 including from about 0.05 to about3 weight percent, based on the total weight of the composition ofisopropyl stearate.

15. A package comprising a pressure-tight container having avalve-controlled outlet and containing a hairsetting compositioncomprising:

a. about 35.5 to about 65 weight percent, based on the total weight ofthe composition, of the solution defined in claim 12, and

b. about 35 to about 64.5 weight percent, based on total weight of thecomposition of isopropyl stearate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,862,306 Dated January 21, 19 25 I InV n Tra .Tnrdan R1 m-k at a! It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 2, line 45, "breaker" should be "beaker;

Column 3, in the formula, add "Unit Ia and Unit 11a" as shown below'.

- CH-CH2--CH-(|1H-- and iT-ICH CHCH o o=c c=0 o o=c I .i O 2 Unit Ia fUnit 11a Column 4, line 60, "hydroxyalkyl" is misspelled;

Column 7, line 49, "waterinsoluble" should be hyphenated.

- Signed and sealed this 1st day of rpril 1975.

SEAL) fattest:

, C. I-IARSHALL DANN 11 T21 C. I-IASON Commissioner of Patents AttestingOfficer and Trademarks 9 O.S. GOVERNMENT PRINTING OFFICE: I969 0 36 6-334.

2. A hair spray composition as claimed in claim 1 in which from about 5 to 50 percent of the free carboxyl groups of said interpolymer have been neutralized by a member of the group consisting of ammonia, primary, secondary, and tertiary alkylamines, alkanolamines and alkylalkanolamines of the formula
 3. A hair spray composition as claimed in claim 1 in which said alkanol is ethyl alcohol, wherein R1 is stearyl, R2 is ethyl and said alkoxy radical is ethoxy.
 4. A hair spray composItion as claimed in claim 3 wherein from about 10 to 20 percent of the free carboxyl groups of said interpolymer have been neutralized by a member of the group consisting of ammonia, primary, secondary, and tertiary alkylamines, alkanolamines and alkylalkanolamines of the formula
 5. A package comprising a closed container with a valve-controlled outlet holding a composition as defined in claim 1 together with a propellant.
 6. A package comprising a closed container with a valve-controlled outlet holding a composition as defined in claim 2 together with a propellant.
 7. A package comprising a closed container with a valve-controlled outlet holding a composition as defined in claim 3 together with a propellant.
 8. A package comprising a closed container with a valve-controlled outlet holding a composition as defined in claim 4 together with a propellant.
 9. A package as defined in claim 7 in which said composition includes isopropyl stearate in an amount from about 0.05 to about 20 percent of the weight of the interpolymer used in said package.
 10. A package as defined in claim 8 in which said composition includes isopropyl stearate in an amount from about 0.05 to about 20 percent of the weight of the interpolymer used in said package.
 11. A hair spray composition comprising an ethyl alcohol solution containing from about 0.05 to about 20 percent by weight of a water-insoluble partial ester of an interpolymer of equimolar amounts of maleic anhydride and a mixture of from 2 to 75 percent by weight of stearyl vinyl ether and from 25 to 98 percent by weight of ethyl vinyl ether based on the total weight of the ether mixture, in which interpolymer from 40 to 60 percent of the total carboxyl groups present in said modified interpolymer are reacted with ethyl alcohol to form said ester; said interpolymer having a Brookfield viscosity from about 200 cps. to 3,000 cps. using a No. 2 spindle at 25*C. and at 30 percent concentration in ethanol with a 250 cc. beaker, the percentage being based on the weight of the total solution.
 12. A hair spray composition as defined in claim 11 wherein from about 10 to 20 percent of the free carboxyl groups have further been reacted with a member of the group consisting of ammonia, primary, secondary, and tertiary alkylamines, alkanolamines and alkylalkanolamines of the formula
 13. A package comprising a pressure-tight container having a valve-controlled outlet and containing a hair-setting composition comprising: a. about 35.5 to about 65 weight percent, basEd on the total weight of the composition, of the solution defined in claim 11, and b. about 35 to about 64.5 weight percent, based on the total weight of the composition, of a propellant.
 14. A package as defined in claim 13 including from about 0.05 to about 3 weight percent, based on the total weight of the composition of isopropyl stearate.
 15. A package comprising a pressure-tight container having a valve-controlled outlet and containing a hair-setting composition comprising: a. about 35.5 to about 65 weight percent, based on the total weight of the composition, of the solution defined in claim 12, and b. about 35 to about 64.5 weight percent, based on the total weight of the composition, of a propellant.
 16. A package as defined in claim 15 including from about 0.05 to about 3 weight percent, based on the total weight of the composition of isopropyl stearate. 